Chemical process and product



the pyrolysis Patented Nov. 6, 1945 UNITED STATES PATENT OFFICE".

CHEMICAL PROCESS AND PRODUCT Alger L. Ward, Bala-Cynwyd, Pa., assignor to The United Gas Improvement Company, a corporation of Pennsylvania No Drawing. Application June 4, 1943, Serial No. 489,695

. 7 Claims.- 01. 260-619) of aryl substituted phenols. ,More particularly,

itrelates tothe production of aryl substituted phenols by reacting phenols with unsaturated aromatic hydrocarbons including unsaturated aromatic hydrocarbons boiling in the range from 183 to 200 C. and obtained from light oil from of petroleum oil.

The lower boiling condensate and the distillate from the tar produced in the manufacture of carburetted water gas, oil gas, and the like, which The entire'portion of the light oil containing aromatic unsaturated hydrocarbons and including unsaturated aromatic hydrocarbons bOlllng (in the range from 183 to 200 C., may be reacted involve the pyrolysis of petroleum, is termed light 7:185

oil. The higher boiling portion of the light oil contains avariet'y' of unsaturated aromatic hydrocarbons mixed with saturated aromatic hydrocarbons of neighboring boiling points.

1 For :instance, the higher boiling portion of a light oil produced in the manufacture of oil gas may contain styrene, ortho; para, and meta methyl styrene, indene, and other unsaturated aromatic hydrocarbons in admixture with the xylene's, cumen, pseudo-cumene, durene, and possibly other saturated aromatic hydrocarbons. These unsaturated hydrocarbons may be concentrated' by further fractionation of the higher boiling portion of the light oil. For instance, a light oil produced in the manufacture of oil gas has been fractionated as follows to concentrate the followin unsaturated aromatic hydrocarbons:

'- Cut points, C.

Styrene forerunnings 135 to 140 Styrene 140 to 150 Unsaturates A1 150 to 160 Unsaturates A2 160 to 167 Methyl styrene group 1 167 to 172 Methyl styrene group 2 172 to 175 Indene group 175 to" 183 Unsaturates B1 183 to 190 Unsaturates B2 190 to 200 The letters A1, A2, B1, and 132, refer to unsaturated aromatic hydrocarbons or mixtures of such unsaturates, not definitely identified.

' According to the present invention, unsaturated aromatic hydrocarbons including unsaturated aromatic hydrocarbons boiling in the range from 183 to200 C. obtained from'light oil from the pyrolysis of petroleum oil, are reacted with phenols in the. presence of a mineral acid catalyst, under controlled temperature conditions to produce aryl substituted phenols.

' with phenols to give mixed aryl substituted phenols corresponding to the various aromatic unsaturates contained therein, or preferably the light oil may be fractionated to concentrate the unsaturated aromatic hydrocarbons boiling in the range from 183 to 200 C. individually or in groups and phenols reacted with the unsaturated aromatics in such fractions to give substituted phenols or groups of substituted phenols of greater or lesser purity.

For example, prior to reaction, with a phenol, the light oil of the class described may be fractionated to yield a fraction having the preponderant portion ofits unsaturation in the form of unsaturated aromatic hydrocarbon material boiling in the range from 183 to,200 C. The concentration may be such as to yield a lightoil fraction having its 10% and boiling points within the recited range, and further the concentration may be such as to yield a light oil fraction boiling substantially completely within the recited range.

The unsaturation contained in the light oil and boiling within the range from 183 to 200 C. may

be subdivided as desired and the divisions separately reacted with a phenol. For example, it may be advantageous to react a phenol with a light oil fraction, the unsaturation of which is predominantly in the form of unsaturated aromatic hydrocarbon material boiling in the range from 183 to C. The concentration of this material may be such that the 10% and 90% boiling points of the fraction fall between 183 and 190 C. Further, the concentration may be such that substantially the entire fraction boils between 183 and 190 C.

Likewise a phenol may be reacted with a light oil fraction having the preponderant portion of its unsaturation in'the form of unsaturated aromatic hydrocarbon material boiling in the range from 190 to 200 C. inclusive. The concentra-' tion may be such, that the 10% and 99% boiling points of this fraction fall between 190 and 200 0. Further, the concentration may be such that sub-stantially all of the fraction boils betweeri190 and 200 (3'.

It may be desirable in the case of highly concentrate'd individual unsaturates or groups, to add an inert solvent such as a saturated hydrocarbon prior to reaction with the phenol.

' for 2 hours.

By phenols, I intend to mean the mono and polyhydroxy derivatives of benzene and its homologues, such as for instance, phenol, cresol, resorcinol, pyrogallol, hydroquinone, pyrocatechol, naphthols, and the like, and substitution products of such compounds. As examples of acids suitable as catalysts for the reaction, sulphuric acid and phosphoric acid may be mentioned.

I have found that the aryl substituted phenols produced in the performance of my invention may be reacted With aldehydes to form resins which are soluble in drying oils, such as linseed oil and tung oil. This characteristic gives them great value for use in varnishes and lacquers in which the usual phenol aldehyde condensation products cannot be used due to their incompatibility with linseed oil and tung oil.

By aldehydes, it is intended to mean the aldehydes customarily employed in the production of phenol aldehyde condensation products of which, for example, formaldehyde and furfural may be preferred because of their relative cheapness.

I have found that in the performance of my invention, in addition to producing valuable aryl substituted phenols, the saturated aromatic hydrocarbons contained in such light oil fractions from the pyrolysis of petroleum may be recovered in a state of purity which requires little 01 no washing, and therefore obviates the large wash losses which arise in the washing of these saturated aromatic hydrocarbons in the presence of the unsaturates.

I have further found that by controlling the concentration of the phenol with respect to the unsaturated aromatic hydrocarbons contained in such light oil fractions, the proportion of the mono substituted aryl phenols with respect to diand trisubstituted phenols may be controlled, increasing excesses of phenol giving higher proportions of mono-substituted products.

The invention will be further understood by reference to the following illustrative examples:

EXAMPLE 1 Six mols of phenol (564 grams) were weighed into a three necked flask equipped with a stirring device, a dropping funnel and a thermometer. To this was added 0.6 cc. of 96% H2804. To this was added 453 grams of a light oil hydrocarbon fraction obtained during a fractional distillation of light oil produced in the manufacture of oil gas by taking a cut over the temperature range 184-190 C. This hydrocarbon fraction contained 57.4% of unsaturated materials by bromine analysis (the unsaturated material being arbitrarily, for purposes of calculation, to be monoolefinic and having an average molecular weight of 130) and the weight used contained approximately 2 mols of reactive hydrocarbon material. This addition was performed dropwise with vigorous agitation. To facilitate agitation at the start of the reaction, the phenol was melted by heating it on a water bath to about 42 C.

By variation of the rate of addition of the hydrocarbon fraction, the temperature was maintained at approximately 45 C. during the entire time the hydrocarbon was being added to the phenol-catalyst mixture. The time required for this addition of hydrocarbon material was 2 to 2.5 hours.

When addition of the hydrocarbon fraction had been completed, heat was applied. The material was kept at a temperature of 130-160 C.

After cooling to 100 C., the sulfuric acid in the mixture was neutralized by adding the calculated quantity of NazCOa dissolved in a few cc. of water.

The purification of the desired condensation product and the recovery of the excess phenol and saturated hydrocarbon was accomplished as follows:

Without further washing or other treatment, the reaction mixture was distilled. After distilling over about 591 grams of unreacted phenol and saturated hydrocarbons, a fraction was taken distillingover in the range -200 C. at 4-6 mm absolute pressure, which weighed 288 grams, about 64% of theory. This fraction was a viscous, oily liquid, phenolic in nature as shown by subsequent tests. A solid residue remained in the distillation flask.

The excess phenol may be separated from the unreacted hydrocarbon by known methods.

The material distilling over in the 155-200" C.

range at 4 to 6 mm. pressure, had the following physical properties.

Color (Gardner-Holdt) 5 Sp. gr. D 20/4 1.0748 N 20/1) 1.5872 Mol. weight. 196.9 Zerewitinoff value per cent 85.4

This phenolic material evidently comprises a mixture of aryl substituted phenols, produced by reaction of the phenol with the aromatic unsaturates of this light oil cut.

EXAMPLE 2 12 mols of phenol (1128 grams) were weighed into a 3 necked flask equipped with a stirring device, a dropping funnel and a thermometer. To this was added 1.2 cc. of 96% H2804. To this was added 769 grams of a light oil hydrocarbon fraction obtained during a fractional distillation of a light oil produced in the manufacture of oil gas by taking a cut over the temperature range 200 C. This hydrocarbon fraction contained 67.6% of unsaturated materials by bromine analysis (the unsaturated material being arbitrarily calculated as mono-olefinic and having an average molecular weight of 130) and the weight used contained therefore about 4 mols of reactive hydrocarbon material. This addition was performed dropwise with vigorous agitation. To facilitate agitation at the start of the reaction, the phenol was melted by heating it on a water bath to about 42 C.

By variation of the rate of addition of the hydrocarbon fraction, the temperature was maintained at approximately 45 C. during the entire time the hydrocarbon was being added to the phenol-catalyst mixture. The time required for this addition was 6-7 hours.

When the addition of the hydrocarbon fraction had been completed, heat was applied. The material was kept at a temperature of 130-160 C. for 2 hours. After cooling to 100 C., the sulfuric acid in the mixture was neutralized by adding the calculated quantity of NazcOa dissolved in lfew cc. of water.

The purification of the desired condensation product and the recovery of the excess phenol and saturated hydrocarbon was accomplished as follows:

Without further washing or other treatment, the reaction mixture was distilled. After collecting about 1013 grams of unreacted phenol and saturated hydrocarbons, a fraction was taken distilling over in the range of ISO-200 C. at 4-6 mm. absolute pressure, which weighed 569 grams, about 63% of theory.

This fraction was a viscous, oily liquid, phenolic in nature as shown by subsequent tests. A solid residue (236 grams) remained. This residue quite probably has value from its resinous properties.

The non-reacted hydrocarbon may be separated from the unreacted phenolby conducting a fractional distillation.

The material distilling over in the range 160- 200 C. at 4 to 6 mm. absolute pressure, had the following physical properties:

Color (Gardner-Holdt) 7 Sp. gr. D 20/4 1.0636 N ZO/D 1.5830 Mol. weight 195 Zerewitinoff value percent 85 This phenolic material evidently comprises a mixture of aryl substituted phenols produced by reaction of the phenol withthe aromatic unsaturates in this light oil cut.

Referring to Examples 1 and 2 the following table gives properties of the distillation residues produced therein.

Table Descrip- 33, 35, 53133. Example tion of uner pressure Other properties saturates initial dist.

point C. l B1 24 200 Dark, resinous, tacky,

solid. 2 B-Z 59 200 D0.

tions resulting in the production of considerable proportions of both mono and di-substituted products.

For example, a molar ratio of phenol to fraction unsaturation (considered arbitrarily for purposes of calculation as mono-olefinic material of average molecular weight of 130) of 5 to 1 may result in the production of mono and di-substituted products in a ratio of the order of to 1. On the other hand, a molar ratio of phenol to fraction unsaturation of 1 to 1 (calculated as above) may produce mono and di-substituted products in a ratio of less than 2 to 1.

Thus varying proportions of mono and di-substituted phenols may be secured by varying the ratio of the quantities of the respective reactants employed.

EXAMPLE 3 To two mols of phenol containing 0.2% by weight of H2504 is added slowly 1 mol of aromatic hydrocarbon unsaturation boiling preponderantly between 183 and 200 C. (calculated arbitrarily as mono-olefinie and of average molecular weight of 130) and contained in a light oil fraction obtained in the pyrolysis of petroleum oil. The temperature is kept-below 50 C. by regulation of therate of addition. When the lightoil fraction is all added the mass is heated to -150 C. for2 hours with agitation. After neutralization of the H2504 with the calculated amount of NazCOa solution, the product is fractionally distilled. The fraction distilling above 200 C. will be found to contain the di-substituted phenol material.

It will be seen from the examples given above, that the process of the invention provides a simple and inexpensive separation of the products of the reaction.

After neutralization of the small quantity of acid, it is only necessary to distill the products to recover separately the water, the unreacted phenol and hydrocarbons, and to separate the mono-aryl phenol from di-aryl phenols and any higher substitution products, which are less valuable products. It is not necessary to wash out the acid catalyst prior to distillation because of the small quantity employed. The unreacted hydrocarbon material and unreacted phenol may be readily separated by known means.

The procedure permits the separate recovery of the saturated aromatic hydrocarbons of these light oil fractions obtained in the pyrolysis of petroleum, which contain considerable concentrations of aromatic unsaturates without the large wash losses incident to washing out the aromatic unsaturates and further provides for recovering the aromatic unsaturates as valuable aryl phenols.

For example, in the production of aryl substituted phenols from the light oil unsaturation in the boiling range from 183 to 200 0., recoveries of saturated aromatic hydrocarbons containing little or no olefinic contamination are possible by fractional distillation of the product followed by separation of the unreacted phenol and the unreacted hydrocarbons.-

As stated before, the aryl phenols produced in accordance with the present invention may be reacted with aldehydes to produce substituted phenol-aldehyde resins which are compatible with drying oils, such as linseed oil and tung oil.

EXAMPLE 4 In a laboratory preparation of a varnish resin approximately 280 grams of the mono-substituted product phenol made from about 160 to 200 C. at 2-5 mm. pressure are used. This is equivalent to 1 4 mols on the assumed average molecular weight of for the original unsaturates. The phenol is reacted with 2 /2 mols ('75 grams) of formaldehyde which is used in the form of an approximately 37% aqueous solution. The phenol and formaldehyde, together with two grams of oxalic acid are agitated in a flask provided with a reflux condenser at reflux temperature for approximately 24 hours. The formaldehyde is added step-wise; one-half being added initially, onequarter after eight hours and one-quarter after sixteen hours. At the expiration of the heating period the reflux condenser is removed and the resin is steamed for about two hours at approximately 200 C. and 50 mm. pressure. The steam is discontinued but the vacuum is left on the system to remove any small quantity of moisture present. The resin is poured out of the flask while still molten, and allowed to cool. The hardened resin is crushed and sieved.

The resin will be iound compatible with linseed and tung oils and may be cooked with these and other drying oils to form varnishes.

The compatibility of these resins with the usually employed drying oils, linseed oil and tung oil. is. an extremely avaluable 1 characteristics It opens the door to the employment of phenol aldehyde" condensation products in coating compositions, such as drying oil varnishes, and affords a new utilization for the unsaturated aromatic hydrocarbons contained in light oil from petroleum pyrolysis, of which there is an extremely large potential supply. 1

The process herein described also affords a more economical method of recovering the saturated aromatic hydrocarbons accompanying the unsaturated aromatic hydrocarbons in such light oil.

It is to be understood that the above particular description is by way of illustration and that changes, omissions, additions, substitutions, and/r modifications may b made within the scope of the claims without departing from the spirit of the invention which is intended to be limited only as required by the prior art.

I claim: I a

1. A process comprising reacting a phenol with a light oil fraction containing unsaturated hydrocarbon material boiling within the range from 183 to 200 0., said reaction taking place in the presence of a condensation catalyst, and said light oil having been obtained from products of pyrolysis of petroleum oil.

2. A process comprising condensing a phenol in the presence of a mineral acid catalyst with a light oil fraction containing unsaturated aromatic hydrocarbon material which boils in the range from 183 to 200 (3., said light oil having been obtained from products of pyrolysis produced in the manufacture of combustible gas by a process involving the thermal decomposition of petroleum oil.

3. A process for producingaryl substituted phenol material comprising reacting a phenol in the presence of a mineral acid catalyst with a light .oil fraction boiling preponderantly-in the range from 183 to 200 C.;-and 'containingunsaturated aromatic hydrocarbon material boilin within said range, said light oil having been separated from products of pyrolysisv obtained in combustible gas manufacture involving the thermal decomposition of petroleum oil.

. 4. A process for producing aryl substituted phenol material comprising reacting phenol in the presence of a mineral acid catalyst with a light oil fraction having 10% and boiling points Within the range irom l83 to200 C. and containing aromatic unsaturation boiling within said range, said light oil having been recovered from petroleum pyrolysis products.

' 5. A process for producing aryl phenol material comprising condensing a phenol in the presence of a mineral acid catalyst with a light oil fraction boiling preponderantly within the range from 183 to 190 C. and containing aromatic unsaturation boiling in said range, said light oil having been obtained from products of petroleum oil pyrolysis. 6. A process for producing aryl phenol material comprising condensing a phenol with a light oil fraction the preponderant part of which boils'in e r n to 00 C, and which contains aromatic unsaturation which boils within said range, said light oil having been obtained from products of pyrolysis of petroleurri'oil. 1 1

'7. A process for producing aryl phenol material comprising condensing phenol in the presence of sulfuric acid as a catalyst with a fraction of a light oil obtained from petroleum oil pyrolysis products, said; fraction containing unsaturated aromatic hydrocarbon material which boils within the range from 183 to 200 0., said condensation being effected under. temperature conditions of from approximately C. to approximately C.

ALGER L. WARD; 

